US4014926A - Fluorinated sulfonic acids and derivatives thereof - Google Patents

Fluorinated sulfonic acids and derivatives thereof Download PDF

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Publication number
US4014926A
US4014926A US05/642,271 US64227175A US4014926A US 4014926 A US4014926 A US 4014926A US 64227175 A US64227175 A US 64227175A US 4014926 A US4014926 A US 4014926A
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Prior art keywords
sub
hydrogen
methyl
compound
propionamide
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US05/642,271
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English (en)
Inventor
Robert Ernest Arthur Dear
Eduard Karl Kleiner
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Novartis Corp
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Ciba Geigy Corp
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Priority to NLAANVRAGE7614059,A priority Critical patent/NL171267C/xx
Application filed by Ciba Geigy Corp filed Critical Ciba Geigy Corp
Priority to US05/642,271 priority patent/US4014926A/en
Priority to CH1557676A priority patent/CH622246A5/de
Priority to DE2656744A priority patent/DE2656744C3/de
Priority to FR7637989A priority patent/FR2335500A1/fr
Priority to IT52642/76A priority patent/IT1069080B/it
Priority to GB52609/76A priority patent/GB1531838A/en
Priority to CA268,118A priority patent/CA1089465A/en
Priority to NLAANVRAGE7614059,A priority patent/NL171267B/xx
Priority to BE173347A priority patent/BE849505A/xx
Priority to JP51152780A priority patent/JPS5277013A/ja
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Publication of US4014926A publication Critical patent/US4014926A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
    • C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
    • C07C309/10—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
    • C07C309/15—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton the nitrogen atom of at least one of the amino groups being part of any of the groups, X being a hetero atom, Y being any atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/20—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic unsaturated carbon skeleton

Definitions

  • the present invention is directed to novel fluorinated alkylamido sulfonic acids and salts of the formula ##STR2## wherein
  • R f is a straight or branched chain perfluoroalkyl of 1 to 18 carbon atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbons.
  • R 1 is hydrogen or lower alkyl
  • R 2 , R 4 and R 5 are independently hydrogen or alkyl group of 1 to 12 carbons
  • R 3 is hydrogen, alkyl of 1 to 12 carbons, phenyl, tolyl or pyridyl,
  • R 6 is a straight or branched chain alkylene of 1 to 12 carbons, alkylenethioakylene of 2 to 12 carbons, alkyleneoxyalkylene of 2 to 12 carbon atoms or alkyleneiminoalkylene of 2 to 12 carbon atoms where the nitrogen atom is secondary or tertiary, and
  • M is hydrogen, a monovalent alkali metal, an alkaline earth metal, an organic base or ammonium, and
  • N IS AN INTEGER CORRESPONDING TO THE VALENCY OF M, i.e., 1 or 2.
  • the alkyl groups of R 2 , R 4 and R 5 can be branched or straight chain alkyl of 1 to 18 carbons or cycloalkyl of 3 to 8 carbons. Illustrative examples of such groups are methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, n-amyl, tert-amyl, and the various isomers of octyl, decyl and dodecyl, but methyl is preferred. Most preferably R 4 and R 5 are hydrogen and R 2 is methyl.
  • the group R 3 is preferably alkyl and most preferably methyl.
  • the group R 1 is hydrogen or lower alkyl having 1 to 4 carbons, and preferably hydrogen or methyl, and most preferably hydrogen.
  • the fluorinated alkylamido sulfonic acids and their salts of this invention can be made by the base catalyzed addition reaction of a thiol, R f --R 6 SH, to an alkenylamidosulfonic acid salt of the formula ##STR3## where M is a monovalent alkali metal, an alkaline earth metal, a common organic base or ammonium.
  • the alkali metals particularly useful are sodium, potassium and lithium.
  • M can also be an alkaline earth metal, especially magnesium, calcium, barium, zinc, cadmium or mercury.
  • M can also be derived from organic bases such as trialkylaryl ammonium hydroxides such as benzyl trimethylammonium hydroxide or tetraethylammonium hydroxide, tertiary amines ##STR4## where the R groups are lower alkyls, metal alkoxides, such as sodium methoxide or potassium t-butoxide, aryl or alkyl lithiums such as phenyl lithium, butyl lithium in nonreactive solvents such as tetrahydrofuran, alkali metal amides such as lithium amide or sodium amide and the like.
  • M is an alkali metal or ammonium
  • n is an integer corresponding to the valency of M.
  • perfluoroalkyl thiols employed in the preparation of the compounds of this invention are well known in the prior art.
  • thiols of the formula R f R 6 --SH have been described in a number of U.S. patents including U.S. Pat. Nos. 2,894,991; 2,961,470; 2,965,677; 3,088,849; 3,172,190; 3,544,663 and 3,655,732.
  • R 6 is alkylene of 1 to 16 carbon atoms and R f is perfluoroalkyl and teaches that halides of formula R f --R 6 --hal are well known; reaction of R f I with ethylene under free radical conditions gives R f (CH 2 CH 2 ) a I while reaction of R f CH 2 I with ethylene gives R f CH 2 (CH 2 CH 2 ) a I as is further taught in U.S. Pat. Nos. 3,088,849; 3,145,222; 2,965,659 and 2,972,638.
  • n 1-3.
  • R' and R" are alkylene of 1 to 16 carbon atoms, with the sum of the carbon atoms of R' and R" being no greater than 25;
  • R f is perfluoroalkyl of 4 through 14 carbon atoms and
  • X is --S-- or --NR'" -- where R'" is hydrogen or alkyl of 1 through 4 carbon atoms.
  • R f is perfluoroalkyl of 4 to 12 carbon atoms. These R f -thiols can be prepared from R f CH 2 CH 2 I and thiourea in very high yield.
  • Alkenylamido sulfonic acids and their salts are well known in the art and have been thoroughly described, for example, in U.S. Pat. Nos. 2,983,712; 3,332,904; 3,506,707 and British Pat. No. 1,090,779; and German Offenlegungsschift No. 2,105,030. Illustrative examples are listed below.
  • 2-acrylamido-2-methylpropanesulfonic acid available, commercially from the Lubrizol Corporation.
  • a base such as a carbonate as, for example, sodium carbonate
  • an intermediate sodium acrylamido sulfonic acid salt is reacted with a base such as a carbonate as, for example, sodium carbonate.
  • a perfluoroalkyl thiol such as 1,1,2,2-tetrahydroperfluorooctane thiol, dissolved in a solvent such as methanol, is introduced into the reaction mixture.
  • the second step is carried out in the presence of a catalytic amount of a base, such as sodium hydroxide, to yield the product.
  • the bases used in Steps 1 and 2 may be the same or they may be different. This has no effect on the course of the reaction, but it is generally more convenient and economical to use bases such that M is the same in both steps. Organic bases are generally used when it is desired to obtain a product with increased solubility over those where M is an alkali metal.
  • Useful solvents for the reaction are those which will dissolve significant amounts of the alkenylamidosulfonic salt and of the mercaptan. Typical of these are the more polar solvents such as water, methanol, ethanol, isopropanol and dimethylformamide.
  • alcohols such as n-propanol, n- and isobutanol, butyl carbitol, ethylene glycol, propylene glycol 1,2 and 1,3, butylene glycol 1,3 and 1,4 2-methyl-2,4-pentanediol, 2,2-diethyl-1,3-propanediol 1,4-cyclohexanedimethanol (cis and trans) and the like; ethers such as glycol ethers (Dowanols, Carbitols and Cellosolves), ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, triethylene glycol, tetraethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, tetrahydrofuran and
  • alcohols
  • Step 1 of the reaction is normally carried out at 0° to 25°, although higher or lower temperatures may be employed.
  • the temperature is controlled at 5°-10° C. This is a simple acid/base neutralization and is thus rapid even at ambient temperatures. Temperatures above about 30° are not recommended since under these circumstances polymerization of the unsaturated amidosulfonic acid may occur. Use of inert gas to blanket the reaction is also useful to prevent unwanted side reactions.
  • Step 2 is the base catalyzed addition of a fluorinated mercaptan to the ⁇ , ⁇ -unsaturated sulfonate formed in Step 1.
  • Step 2 may be carried out at temperatures of 0° to 100°, but to achieve reasonable reaction times, a temperature of 50°-80° is preferred. Under these conditions -- e.g., in refluxing methanol or ethanol -- reaction is complete in two to two and one half hours. At 25° the reaction is considerably slower.
  • the compounds of this invention can be converted to the corresponding sulfones and sulfoxides. This can be accomplished by known oixdation methods, such as reacting the thioether with acetic acid and a peroxide, e.g., H 2 O 2 , as described in greater detail in German OS-DT No. 2,334,889 which is incorporated herein by reference.
  • oixdation methods such as reacting the thioether with acetic acid and a peroxide, e.g., H 2 O 2 , as described in greater detail in German OS-DT No. 2,334,889 which is incorporated herein by reference.
  • 2-Acycrylamido-2-methylpropanesulfonic acid (10.35 g; 0.05 mole) was placed in a 250 ml three-necked flask fitted with a mechanical stirrer, thermometer, nitrogen inlet and a condenser in the reflux position. Dry methanol (50 ml) was added, followed by sodium carbonate (2.76 g; 0.026 mole) over a 15 minute period. After all CO 2 evolution had ceased, 1,1,2,2-tetrahydroperfluorooctane thiol (19.0 g; 0.05 mole), dissolved in a further 50 ml of dry methanol, was added together with 0.04 g (0.0005 mole) sodium hydroxide catalyst.
  • the surfactants of this invention may also be prepared in solution in such a manner that they are suitable for use without isolation of the solid surfactants.
  • 2-Acycrylamido-2-methylpropanesulfonic acid (21.74 g; 0.105 mole) was placed in a 250 ml three-necked flask, equipped as described in Example 1. Water (37 g) was added with stirring, then a cooling bath was placed around the flask and, maintaining the temperature at about 10° C, sodium carbonate (5.62 g; 0.053 mole) was added in portions. After all CO 2 evolution had ceased, the cooling bath was removed and hexylene glycol (40.2 g) was added as a cosolvent.
  • This example illustrates the inverse addition of reactants in the first step.
  • Example 2 Using the equipment described in Example 1, sodium hydroxide (8.6 g of 50% solution; 0.107 mole) was mixed with 29.6 g deionized water in the reaction flask, and the solution was cooled to 0° C. 2-acrylamido-2-methyl propane sulfonic acid (21.7 g; 0.105 mole) was added slowly, as a powder, at such a rate that the ensuing exothermic reaction maintained the system at 3°-10° C. Total addition required about 30 minutes.
  • R f is a mixture as previously defined.
  • magnesium carbonate (4MgCO 3 .Mg(OH) 2 .nH 2 O; assay 41.5% MgO; 3.65 g, 0.038 mole) was added to 25 ml deionized water in the flask.
  • the system was cooled to 2° and 2-acrylamido-2-methyl propane sulfonic acid (15.53 g; 0.075 mole) was added at a rate such that the ensuing exothermic reaction was controlled at about 5°. Good stirring was maintained and the system was placed under a slow stream of nitrogen.
  • 1,1,2,2-tetrahydroperfluorooctane thiol (28.5 g; 0.075 mole) was added followed by 50 g isopropyl alcohol and 2 drops of 50% sodium hydroxide solution as a catalyst. The system then was stirred at 65° for 20 hours and the resulting white emulsion, which was now devoid of mercaptan, was poured into an excess of acetone. The white percipitate which resulted was filtered and dried at 70° and 0.1 mm Hg, to give 41.3 g (91.8% yield) of product.
  • the structure of the product was confirmed by elemental analysis and n.m.r. spectroscopy.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
US05/642,271 1975-12-19 1975-12-19 Fluorinated sulfonic acids and derivatives thereof Expired - Lifetime US4014926A (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
NLAANVRAGE7614059,A NL171267C (nl) 1975-12-19 Werkwijze voor het bereiden van gefluoreerde sulfonzuren en zouten daarvan, alsmede werkwijze voor het bereiden van samenstellingen, die deze verbindingen bevatten.
US05/642,271 US4014926A (en) 1975-12-19 1975-12-19 Fluorinated sulfonic acids and derivatives thereof
CH1557676A CH622246A5 (enrdf_load_stackoverflow) 1975-12-19 1976-12-10
DE2656744A DE2656744C3 (de) 1975-12-19 1976-12-15 Fluorierte Alkylamidoalkansulfonsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
IT52642/76A IT1069080B (it) 1975-12-19 1976-12-16 Acidi alchilammidoalcansolfonici fluorurati procedimento per produrli e composizioni che li contengono
GB52609/76A GB1531838A (en) 1975-12-19 1976-12-16 Fluorinated alkylamidoalkane sulphonic acids process for their manufacture and their use
FR7637989A FR2335500A1 (fr) 1975-12-19 1976-12-16 Acides alkylamidoalcane sulfoniques fluores, leur procede de preparation et leur utilisation
CA268,118A CA1089465A (en) 1975-12-19 1976-12-17 Fluorinated alkylamidoalkane sulfonic acids, process for their manufacture and their use
NLAANVRAGE7614059,A NL171267B (nl) 1975-12-19 1976-12-17 Werkwijze voor het bereiden van gefluoreerde sulfonzuren en zouten daarvan, alsmede werkwijze voor het bereiden van samenstellingen, die deze verbindingen bevatten.
BE173347A BE849505A (fr) 1975-12-19 1976-12-17 Acides alkylamidoalcane sulfonique fluores, leur procede de preparation et leur utilisation
JP51152780A JPS5277013A (en) 1975-12-19 1976-12-18 Alkyl amide alkane sulfonic acid fluoride* manufacturing process and use thereof

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US (1) US4014926A (enrdf_load_stackoverflow)
JP (1) JPS5277013A (enrdf_load_stackoverflow)
BE (1) BE849505A (enrdf_load_stackoverflow)
CA (1) CA1089465A (enrdf_load_stackoverflow)
CH (1) CH622246A5 (enrdf_load_stackoverflow)
DE (1) DE2656744C3 (enrdf_load_stackoverflow)
FR (1) FR2335500A1 (enrdf_load_stackoverflow)
GB (1) GB1531838A (enrdf_load_stackoverflow)
IT (1) IT1069080B (enrdf_load_stackoverflow)
NL (2) NL171267B (enrdf_load_stackoverflow)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4070385A (en) * 1973-12-12 1978-01-24 The Lubrizol Corporation Phosphorus, nitrogen and sulfo-containing additives
USRE30142E (en) * 1973-12-12 1979-11-06 The Lubrizol Corporation Phosphorus, nitrogen and sulfo-containing additives
US4399068A (en) * 1977-01-22 1983-08-16 Bayer Aktiengesellschaft Concentrated, aqueous solutions of salts of acetoacetylamino-arylsulphonic acids and method of forming concentrated solutions of azo dyestuffs therefrom
US4404377A (en) * 1982-03-08 1983-09-13 Nalco Chemical Company Heterocyclic/aromatic fluorocarbon surfactants
US4408043A (en) * 1982-03-08 1983-10-04 Nalco Chemical Company Fluorocarbon surfactants
US4431595A (en) * 1980-03-14 1984-02-14 Dainippon Ink & Chemicals, Inc. Fluorine-containing aminosulfonate
US4505990A (en) * 1983-07-14 1985-03-19 Hercules Incorporated Coating compositions
US4594200A (en) * 1984-11-15 1986-06-10 Halliburton Company Compositions for increasing hydrocarbon production from subterranean formations
US4781865A (en) * 1986-09-29 1988-11-01 Ecolab, Inc. Phosphinated and phosphonated sulfonic acids
US4923009A (en) * 1989-05-05 1990-05-08 Union Oil Company Of California Steam enhanced oil recovery processes and compositions for use therein
WO1994013634A1 (en) * 1992-12-08 1994-06-23 Minnesota Mining And Manufacturing Company Fluoroaliphatic radical-containing anionic sulphonamido compounds as surfactans
US5580847A (en) * 1992-03-06 1996-12-03 Nissan Chemical Industries, Ltd. Aqueous ammonia composition
KR100761815B1 (ko) 2006-11-21 2007-10-04 재단법인서울대학교산학협력재단 생물부착 방지용 고분자 및 이를 이용한 생물부착 방지막의형성방법
US20110053810A1 (en) * 2009-09-03 2011-03-03 Halliburton Energy Services, Inc. Fluorosurfactants and Treatment Fluids for Reduction of Water Blocks, Oil Blocks, and/or Gas Condensates and Associated Methods
US20110212320A1 (en) * 2007-08-10 2011-09-01 Greenhill Antiballistics Corporation Composite Material
US8524104B1 (en) 2008-08-28 2013-09-03 Ansul, Incorporated Fluoroalkenyl sulfate surfactants
US9328788B2 (en) 2010-10-18 2016-05-03 Greenhill Antiballistics Corporation Gradient nanoparticle-carbon allotrope-polymer composite material
US12191228B2 (en) 2016-04-06 2025-01-07 Sanctioned Risk Solutions, Inc. Heat dissipation using nanoscale materials

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5660815A (en) * 1995-04-28 1997-08-26 Molecular Biosystems, Inc. Water soluble fluorinated fatty acid sulfonate derivatives useful as magnetic resonance imaging agents

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3235549A (en) * 1962-08-21 1966-02-15 Monsanto Co 2-dioxy-1, 2, 5-oxathiazine compounds and processes for their manufacture
US3544597A (en) * 1969-06-12 1970-12-01 Rohm & Haas Process for manufacturing sulfonated amides
US3798265A (en) * 1969-10-22 1974-03-19 Du Pont Polyfluoroalkoxy alkyl amidocarboxylic acids and salts thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3235549A (en) * 1962-08-21 1966-02-15 Monsanto Co 2-dioxy-1, 2, 5-oxathiazine compounds and processes for their manufacture
US3544597A (en) * 1969-06-12 1970-12-01 Rohm & Haas Process for manufacturing sulfonated amides
US3798265A (en) * 1969-10-22 1974-03-19 Du Pont Polyfluoroalkoxy alkyl amidocarboxylic acids and salts thereof

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE30142E (en) * 1973-12-12 1979-11-06 The Lubrizol Corporation Phosphorus, nitrogen and sulfo-containing additives
US4070385A (en) * 1973-12-12 1978-01-24 The Lubrizol Corporation Phosphorus, nitrogen and sulfo-containing additives
US4399068A (en) * 1977-01-22 1983-08-16 Bayer Aktiengesellschaft Concentrated, aqueous solutions of salts of acetoacetylamino-arylsulphonic acids and method of forming concentrated solutions of azo dyestuffs therefrom
US4431595A (en) * 1980-03-14 1984-02-14 Dainippon Ink & Chemicals, Inc. Fluorine-containing aminosulfonate
US4404377A (en) * 1982-03-08 1983-09-13 Nalco Chemical Company Heterocyclic/aromatic fluorocarbon surfactants
US4408043A (en) * 1982-03-08 1983-10-04 Nalco Chemical Company Fluorocarbon surfactants
US4505990A (en) * 1983-07-14 1985-03-19 Hercules Incorporated Coating compositions
US4594200A (en) * 1984-11-15 1986-06-10 Halliburton Company Compositions for increasing hydrocarbon production from subterranean formations
US4781865A (en) * 1986-09-29 1988-11-01 Ecolab, Inc. Phosphinated and phosphonated sulfonic acids
US4923009A (en) * 1989-05-05 1990-05-08 Union Oil Company Of California Steam enhanced oil recovery processes and compositions for use therein
US5580847A (en) * 1992-03-06 1996-12-03 Nissan Chemical Industries, Ltd. Aqueous ammonia composition
US6201122B1 (en) * 1992-12-08 2001-03-13 3M Innovative Properties Company Fluoroaliphatic radical-containing anionic sulfonamido compounds
WO1994013634A1 (en) * 1992-12-08 1994-06-23 Minnesota Mining And Manufacturing Company Fluoroaliphatic radical-containing anionic sulphonamido compounds as surfactans
KR100761815B1 (ko) 2006-11-21 2007-10-04 재단법인서울대학교산학협력재단 생물부착 방지용 고분자 및 이를 이용한 생물부착 방지막의형성방법
US11718067B2 (en) 2007-08-10 2023-08-08 Greenhill Antiballistics Corporation Composite material
US20110212320A1 (en) * 2007-08-10 2011-09-01 Greenhill Antiballistics Corporation Composite Material
US9060560B2 (en) 2007-08-10 2015-06-23 Greenhill Antiballistics Corporation Composite material
US8524104B1 (en) 2008-08-28 2013-09-03 Ansul, Incorporated Fluoroalkenyl sulfate surfactants
US8669212B2 (en) * 2009-09-03 2014-03-11 Halliburton Energy Services, Inc. Fluorosurfactants and treatment fluids for reduction of water blocks, oil blocks, and/or gas condensates and associated methods
US8772204B2 (en) * 2009-09-03 2014-07-08 Halliburton Energy Services, Inc. Fluorosurfactants and treatment fluids for reduction of water blocks, oil blocks, and/or gas condensates and associated methods
US20120172262A1 (en) * 2009-09-03 2012-07-05 Halliburton Energy Services, Inc. Fluorosurfactants and Treatment Fluids for Reduction of Water Blocks, Oil Blocks, and/or Gas Condensates and Associated Methods
US20110053810A1 (en) * 2009-09-03 2011-03-03 Halliburton Energy Services, Inc. Fluorosurfactants and Treatment Fluids for Reduction of Water Blocks, Oil Blocks, and/or Gas Condensates and Associated Methods
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Publication number Publication date
NL171267B (nl) 1982-10-01
DE2656744A1 (de) 1977-06-30
DE2656744C3 (de) 1980-10-09
JPS5277013A (en) 1977-06-29
FR2335500A1 (fr) 1977-07-15
CA1089465A (en) 1980-11-11
NL171267C (nl)
JPS5725034B2 (enrdf_load_stackoverflow) 1982-05-27
IT1069080B (it) 1985-03-25
DE2656744B2 (de) 1980-02-14
CH622246A5 (enrdf_load_stackoverflow) 1981-03-31
NL7614059A (nl) 1977-06-21
FR2335500B1 (enrdf_load_stackoverflow) 1979-07-13
GB1531838A (en) 1978-11-08
BE849505A (fr) 1977-06-17

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